JPS59179510A - Preparation of ethylene copolymer - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer having improved moldability and mechanical properties, by copolymerizing ethylene with an alpha-olefin in the presence of a catalyst prepared by blending a reaction product of a Mg alkoxide, a halogenated hydrocarbon, an electron donor, and a Ti compound with an organoaluminum compound. CONSTITUTION:Ethylene is copolymerized with an alpha-olefin (e.g., 1-butene, etc.) using a catalyst consisting of (A) a catalytic component obtained by reacting (i) a magnesium alkoxide (e.g., magnesium ethoxide, etc.) with (ii) a halogenated hydrocarbon (e.g., hexachloroethane, etc.), (iii) an electron donor compound (e.g., ethyl benzoate, etc.), and (iv) a titanium compound (e.g., titanium tetrachloride, etc.) and (B) an organoaluminum compound (e.g., triethylaluminum, etc), to give the desired copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a method for producing an ethylene copolymer, and in particular to a specific ethylene copolymer composition obtained by the method,
More specifically, the present invention relates to an ethylene copolymer composition having a wide molecular weight distribution and excellent moldability and mechanical properties.

Background Art Low-density ethylene copolymer obtained by copolymerizing ethylene and α-olefin (e.g., propylene, butene-1, hexene-1, octene-1,4-methyl, pentene-1, etc.) at low pressure. Although it has the same density as low-density polyethylene produced by the conventional high-pressure process, it has excellent mechanical properties and is expected to be used in new fields.

However, low-pressure low-density polyethylene has poor melt rheological properties when compared to high-pressure low-density polyethylene; for example, it requires a large amount of electrical energy during inflation, the discharge lid is reduced, bubble stability is poor, and high speed There are problems such as the formation of shark skin on the surface of the film during processing, and similar problems arise in blow molding or injection molding. Attempts have been made to deal with these problems by modifying extruders, screws, guides, etc., but these require a great deal of expense and no fundamental solution has yet been reached.

In order to improve such moldability, it is easy to think of broadening the molecular weight distribution, but in order to improve the essential rheological properties as mentioned above, it is necessary to consist of a (ultra) high molecular weight component and a low molecular weight component. A wide molecular weight distribution is required.

Therefore, it has been considered difficult to produce such (ultra) high molecular weight or low molecular weight low density polyethylene on a commercial scale due to catalyst and process problems. In other words, in the gas phase method, since the amount of recycled gas is extremely large, it takes a lot of time to change the partial pressure of hydrogen, which is the molecular ik regulator contained in this gas, and a large amount of non-standard products are produced during that time. Therefore, it is not economically realistic. Furthermore, in the solution method, when producing (ultra)high molecular weight polyethylene, the viscosity of the solution increases significantly, so the polymer concentration must be diluted considerably, which deteriorates productivity and is not practical. Furthermore, when producing low-density polyethylene using the slurry method, especially low-molecular-weight low-density polyethylene, a large amount of soluble polymer is produced in the dispersion medium, resulting in fouling in the reaction vessel and adhesion of polymer particles to each other. Due to this problem, it is currently difficult to efficiently produce polyethylene with a sufficiently low density.

In order to obtain a broad-b polyolefin with a molecular weight distribution, methods using multistage polymerization and blending have been known.

However, in order to produce low-density polyethylene copolymer compositions with a wide molecular weight distribution, the selection of catalysts and processes is important, and at present no production technology has been established on a commercial scale. .

Recently, attempts have been made to blend low-density polyethylene copolymers produced using supported Ziegler catalysts to create low-density poly, 1-tyrene copolymer compositions with a wide molecular weight distribution, for example in JP-A-57-59943. , 57-126854
It is disclosed in the publication number etc. However, even with these attempts, it is difficult to obtain a composition with sufficiently good moldability.

Disclosure of the Invention Purpose of the Invention The object of the present invention is to provide an ethylene polymer having a wide molecular weight distribution and excellent properties in both mechanical properties and moldability. As a result of extensive studies, the present inventors discovered that a composition obtained by blending an ethylene copolymer produced using a polyolefin production catalyst previously invented could achieve the object of the present invention. The invention has been completed.

Summary of the invention That is, the summary of the present invention is that magnesium alkoxide,
A method for producing an ethylene copolymer comprising copolymerizing ethylene and α-olefin using a catalyst component formed by contacting a halogenated hydrocarbon, an electron donating compound and a titanium compound, and a catalyst formed of an organoaluminum compound. A) Melt index 0.001 to 1f/10 min, density 0. ．． 900-0.94017 cm3 copolymer 10
~60% by weight, and B) melt index 50 ~ 2,000 r/10 min,
Copolymer 40 with density 0.920-0.95Of/α3
A melt index of 0.01 to 60 f/10 min consisting of 90% by weight, preferably a ratio of melt viscosities at a shear rate of 0.1 rad/sec and 500 rad/sec η0.
1/η500 converted into melt index 12/10 minutes (η01/η500) M1=1 is 20 or more, and the density is 0910 to 0,940? /cm'' has a wide molecular weight distribution and excellent mechanical properties and moldability.

Raw Materials for Preparing Catalyst Components Each raw material used in preparing the catalyst component used in the present invention will be explained.

(]) Magnesium alkoxide The magnesium alkoxide used in the present invention is represented by the general formula Mg (O)1 ) (OR'). In the formula, R and )(' represent 1 to 20 carbon atoms,
Desirably 1 to 10 alkyl, alkenyl, cycloalkyl, aryl, or aralkyl groups. Further, R and R' may be the same or different.

Examples of these compounds include Mg(OC'f(s)t
+Mg(OCzHs)z +Mg(OCHs)(OCt
Hs) + Mg(Ol-C's"γ)2゜Mg(○C3
H7)2 to +λ (OC4Hg )2 , Mg (O1
-C4I(0)2.

Mg(QC4Ho)(Oi C4H+J+Mg(OC
Jo) (○sec C4HQ)11Ag(OC1!1H
1i beauty+”g (oc6II?)2t Mg (O
cean )2 + Mg(OCeHs )2 , Mg(
OC6H4CH,)2 , Mg(OCH2(4H5)2
etc. can be mentioned.

When these magnesium alkoxides are used, it is desirable to dry them, and it is particularly desirable to dry them by heating under reduced pressure. Furthermore, it is preferable to use one that has been dried and then ground.

(2) Halogenated hydrocarbon The halogenated hydrocarbon used in the present invention has 1 to 1 carbon atoms.
Mono- and polyhalogen substituted products of two saturated or unsaturated aliphatic, alicyclic and aromatic hydrocarbons. Specific examples of these compounds include, for aliphatic compounds, methyl chloride, methyl bromide, methylene ioguide, methylene chloride, methylene bromide, methylene ioguide, chloroform, bromoform, iodoform, carbon tetrachloride, carbon tetrabromide, carbon iodide, ethyl chloride,
Agedichloroethane, 1,2-dibromoethane, 1.2
-Short ethane, methyl chloroform, methyl bromoform, methyl iodoporm 1.1.2-), dichloroethylene, 1,1.2-) sobromoethylene, 1,1
, 2.2-tetrachloroethane, pentachloroethane, hexachloroethane, hexabromoethane, n-propyl chloride, 1,2-dichloropropane, hexachloropropylene, octachloropropane, tetrachlorobutane, and salt-accumulated paraffin. , alicyclic compounds include chlorocyclopropane, tetrachlorocyclopenkune, l\xachloropentadiene, and hexachlorocyclohexane; aromatic compounds include chlorbenzeno, bromobenzene,
Examples include 0-dichlorobenzene, p-dichlorobenzene, hexachlorobenzene, hexabromobenzene, pensitrichloride, p-chlorobenztrichloride, and the like. Not only one kind but also two or more kinds of these compounds may be used.

(3) Titanium compounds Titanium compounds are divalent, trivalent, and tetravalent titanium compounds, examples of which include titanium tetrachloride, titanium tetrabromide, trichloroethoxytitanium, trichlorobutoxytitanium, and dichlorjetoxy titanium. Titanium, dichlordibutoxytitanium, dichlordiphenoxytitanium, chlortriethoxytitanium, chlortributoxytitanium, tetrabutoxytitanium, titanium trichloride and the like can be mentioned. Among these, tetravalent titanium/S chlorides such as titanium tetrachloride, trichloroethoxytitanium, dichlorodibutoxytitanium, and dichlordiphenoxytitanium are preferred, and titanium tetrachloride is particularly preferred.

The electron-donating compounds used in the present invention include carboxylic acids, carboxylic esters, alcohols, ethers, ketones, amines, amides, nitriles, aldehydes, alcoholates, organic groups and carbon or phosphorus, arsenic and antimony compounds, bound through oxygen;
Preferred among these are phosphoamides, thioethers, thioesters, and carbonate esters,
Those used are carbonic acid esters, alcohols, and ethers.

Specific examples of carboxylic acid esters include butyl formate, ethyl acetate, butyl acetate, ethyl acrylate, ethyl dichloromethane, isobutyl isobutyrate, methyl meccrylate, diethyl maleate, diethyl filate, ethyl cyclohexanecarboxylate, and benzoic acid. Examples include, but are not limited to, ethyl acid, ethyl p-methoxybenzoate, methyl p-methylbenzoate, ethyl p-tertiary butylbenzoate, dibutyl phthalate, diallyl phthalate, ethyl α-naphthoate, etc. It is not something that will be done. Among these, alkyl esters of aromatic carboxylic acids, particularly alkyl esters of benzoic acid or nuclear substituted benzoic acids having 1 to 8 carbon atoms such as p-methylbenzoic acid and p-methoxybenzoic acid, are preferably used.

Alcohols are represented by the general formula ROH.

In the formula, R is alkyl, alkenyl, cycloalkyl, aryl, or aralkyl having 1 to 12 carbon atoms.

Specific examples include methanol, ethanol, propatool, isoproptool, butanol, isobutanol, pentanol, hexanol, octatool, 2-
These include ethylhegisanol, cyclohexynol, benzyl alcohol, and allyl alcohol. Ether cheeks are represented by the general formula ROR'. In the formula, R and R' are alkyl, alkenyl, cycloalkyl, aryl, and aralkyl having 1 to 12 carbon atoms, and R and R' may be the same or different. Cyclic ethers can also be used. Specific examples include diethyl ether, diisoamyl ether, dibutyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylphenyl ether, diallyl ether, ethyl allyl ether, butyl alif l/ether, diphenyl ether, anisole, ethylphenyl ether, Tetrahydrofuran, 1
, 4-dioxane, etc.

Preparation method of catalyst component The catalyst component used in the present invention can be obtained by contacting magnesium alkoxide, halogenated hydrocarbon, N, compound, and titanium compound. Magnesium alkoxide, halogenated hydrocarbon,
The method of contacting the electron-donating compound and the titanium compound is as follows: (1) bringing the magnesium alkoxide into contact with the halogenated hydrocarbon, then contacting the electron-donating compound, and then contacting the titanium compound; (2) bringing the magnesium alkoxide into contact with the halogenated hydrocarbon; Contacting an electron-donating compound, then contacting a halogenated hydrocarbon, and then contacting a titanium compound; (3) Contacting a magnesium alkoxide with a halogenated hydrocarbon, then contacting a titanium compound, and then contacting the titanium compound; contacting the compounds, (4) simultaneously contacting the magnesium alkoxide, the genated hydrocarbon, and the electron-donating compound, and then contacting the titanium compound; (5) bringing the magnesium alkoxide, the genated hydrocarbon, and the titanium compound into contact; (6) contacting simultaneously and then contacting an electron donating compound;
(7) Bringing the magnesium alkoxide, the halogenated hydrocarbon, the electron donating compound, and the titanium compound into contact simultaneously. , methods are preferably used, and more preferably methods (1), (
These are methods 2) and (3). The methods (1) to (3) will be explained below.

Method (1)■ Contact of magnesium alkoxide with hydrogenated hydrocarbon The contact between magnesium alkoxide and 710-genated hydrocarbon is carried out using a solid or slurry mixture of magnesium alkoxide and solid or liquid 710-genated hydrocarbon. This can be achieved by mechanically co-pulverizing a mixture of the above, or by simply stirring and contacting the mixture. Among these, a contact method of mechanical co-pulverization is preferred.

As the halogenated hydrocarbon, any of the above compounds may be used, but poly/1 of hydrocarbons having 2 or more carbon atoms may be used.
Zero genide is preferred. Examples of these are 1,2-dichloroethane, 1,1.2-trichloroethane, 1゜1
．． 2-1-dichloroethylene, 1,1,2.2-tetrachloroethane, 1.2,2.2-tetrachloroethane,
Examples include pentachloroethane, hexachloroethane, 1,2-dichloropronodenone, hexachloropropylene, octachloropropane, hexachlorobenzene, and the like.

The contact ratio of magnesium alkoxide and halogenated hydrocarbon is 1 mole of magnesium alkoxide to 0.01 to 20 mole of halogenated hydrocarbon, preferably 0.1 to 20 mole.
It is 20 moles.

In the case of mechanical co-pulverization, the contact between the two can be carried out using an ordinary pulverizer used to obtain a pulverized product. Examples of the pulverizer include a rotary ball mill, a vibrating ball mill, an impact mill, etc. can be mentioned. Co: The pulverization treatment can be carried out, if necessary, under reduced pressure or in an inert gas atmosphere, and in a state substantially free of moisture, oxygen, and the like.

In the case of mechanical co-pulverization, the contact temperature is 0 to 200°C, and the contact time is 0.5 to ion hours. Further, in the case of a contact method of simply stirring, the contact temperature is 0 to 200°C, and the contact time is 05 to 100 hours.

The magnesium alkoxide may be contacted with a magnesium halide before contacting with a halogenated hydrocarbon.

Magnesium halides include magnesium chloride, which is magnesium dil\ride, and magnesium bromide.
, magnesium iodide is preferred, and magnesium chloride is preferred at 1%.

For convenience of use, it is preferable to use powders of these magnesium halides having an average particle size of about 1 to 50 microns, but those with even larger particle sizes can also be used.

Further, these magnesium halides are desirably so-called anhydrous ones that do not substantially contain crystal water. Therefore, when using a commercially available product, heat it at 200 to 600°C in the presence of an inert gas such as nitrogen, or at 100°C under reduced pressure before use.
Although it is preferable to heat the treatment at a temperature of ~400°C, etc., there is no particular limitation.

The contact between the magnesium alkoxide and the magnesium halide is achieved by mixing and stirring them in the presence or absence of an inert hydrocarbon, mechanically co-pulverizing them, and the like.

Examples of inert hydrocarbons include hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, and the like.

The contact ratio between magnesium alkoxide and magnesium halide is 0.1 to 10 mol, preferably 0.3 to 20 mol, of magnesium/X halide per mol of magnesium alkoxide. When contacting is made in the presence of an inert hydrocarbon, it is desirable to use 1 to 1002 of the hydrocarbon per 1001 of the total amount of Red Sea Bream Sil, alkoxide and magnesium halide.

When mechanically co-pulverizing the magnesium alkoxide and magnesium halide, the contact temperature is between room temperature and 200°C.
When mixing and stirring in the presence of the hydrocarbon, it is desirable to carry out the mixing at room temperature to 200°C for 1 to 100 hours. Among these contact methods, a method of mechanical co-pulverization is particularly desirable.

The mechanical co-pulverization method may be carried out in the same manner as the co-pulverization method in the method of contacting magnesium alkoxide and halogenated hydrocarbon.

The magnesium alkoxide previously treated with the magnesium halide as described above is brought into contact with the halogenated hydrocarbon as described above, in which case the tz Ij genide of the one carbon hydrocarbon is also naturally Can be used.

Alternatively, the magnesium alkoxide, the magnesium halide, and the halogenated hydrocarbon may be brought into contact at the same time.

(2) Contact with an electron-donating compound The contact material of magnesium alkoxide and halogenated hydrocarbon (hereinafter referred to as contact material (1)-1) is then brought into contact with an electron-donating compound. The contact material (1)-1 may be cleaned with a suitable cleaning agent, such as the above-mentioned inert hydrocarbon, before being brought into contact with the electron-donating compound.

The contact material (1)-1 and the electron-donating compound may be brought into contact as they are, or may be brought into contact in the presence of an inert hydrocarbon and/or a halogenated hydrocarbon.

Examples of the contact method include a method of mixing and stirring the two, a method of mechanically co-pulverizing the two, and the like.

As the inert hydrocarbon, saturated aliphatic, saturated alicyclic, and aromatic hydrocarbons having a carbon Ra of 6 to 12 such as hexane, heptane, octane, cyclohexane, benzene, toluene, and xylene are preferable (hereinafter referred to as the present invention). In the description, inert hydrocarbons usually refer to these.) Further, as the halogenated hydrocarbon, any compound can be used as long as it is used when brought into contact with the above-mentioned magnesium alkoxide. Contact ratio between contact substance (1)-1 and electron donating compound c, magnesium alkoxide 1
0.001 to 10 mol of electron donating compound per mol, preferably 0.001 to 10 mol, preferably 0. U1 to 5 moles.

In the method of contacting in the presence of a hydrocarbon, when mixing and stirring, it is desirable to use k such that the solid substance in the contact system is 10 to 6002 per 1 part of the liquid substance. The contact temperature is 0 to 200℃
, preferably at 20 to 150°C, and the contact time is 01
~20 hours, preferably 0.5-10 hours. When co-pulverizing mechanically, contact object (1)-11 oay,
The hydrocarbon is 1 to 100! It is desirable to use i', and the contact temperature at this time is room temperature to 200°C, and the contact time is 01 to 1
It is 00 hours.

When contacting an electron-donating compound in the absence of a hydrocarbon, it is preferable to use a method of mechanical co-pulverization.
The contact temperature at this time is preferably room temperature to 200°C, and the contact time is 0.1 to 100 hours.

■ Contact with titanium compound Contact with magnesium alkoxide, halogenated hydrocarbon and electron donating compound (hereinafter referred to as contact (1) -2
The material is then contacted with a titanium compound. Contact article (1)-2 may be cleaned with a suitable cleaning agent, such as the inert hydrocarbons mentioned above, before contacting with the titanium compound.

The contact material (1)-2 and the titanium compound may be brought into contact with each other as they are, but they may be mixed and stirred in the presence of a hydrocarbon and/or halogenated hydrocarbon, or mechanically co-pulverized. It is desirable to do this using a method such as

Hydrocarbons include hekylin, heptano, octane,
Saturated aliphatic, saturated alicyclic and aromatic hydrocarbons having 6 to 12 carbon atoms such as cyclohexane, benzene, ]-toluene and xylene are preferred. Further, as the halogenated hydrocarbon, any compound can be used as long as it is used when brought into contact with the magnesium alkoxide.

The proportion of the contact between the contact material (1)-2 and the titanium compound is at least 0.1 g mole, preferably from 1 to 5 g mole of the titanium compound per 1 gram atom of magnesium in the contact material (1)-2. It is. When the contact is carried out in the presence of a hydrocarbon and/or a halogenated hydrocarbon, the contacting conditions are 0 to 200°C for 0.5 to 20 hours, preferably 60 to 150°C for 1 to 5 hours.

When using a hydrocarbon and/or a halogenated hydrocarbon, the amount of the contact material (1)-2 is 10 to 6001 per 16 of the liquid substance (hydrocarbon and/or liquid halogenated hydrocarbon and liquid titanium compound). It is desirable to use it as follows.

Further, the contact material (1)-2 and the titanium compound may be brought into contact with each other two or more times, and the contact conditions may be the same as those described above.

Method (2) ■ Contact between magnesium alkoxide and electron-donating compound The contact between magnesium alkoxide and 'ft-donating compound is carried out in the presence of an inert hydrocarbon, as in method (1) (■) above. Alternatively, this can be achieved by a method of mixing and stirring, a method of mechanically co-pulverizing, etc. in the absence of such a material. The contact ratio between the magnesium alkoxide and the electron donating compound is 0,001 to 10 moles, preferably 0.01 to 5 moles, of the electron donating compound per mole of magnesium alkoxide.

In a method of contacting in the presence of an inert hydrocarbon,
When mixing and stirring the hydrocarbon, it is desirable to use an amount such that the solid substance in the contact system is 10 to 5,001 parts per iz of the liquid substance, and the contact temperature in this case is 0.
-200°C, preferably 20-150°C, and the contact time is 0.1-20 hours, preferably 0.5-10 hours. In the case of mechanical co-pulverization, it is desirable to use 1002 of magnesium alkoxide and 1 to 1002 of the hydrocarbon, and the contact temperature at this time is room temperature to 200°C, and the contact time is 0.1 to 100 hours.

When contacting an electron-donating compound in the absence of a hydrocarbon, it is preferable to use a method of mechanical co-pulverization.
The contact temperature at this time is preferably room temperature to 200°C, and the contact time is 0.1 to 100 hours.

The magnesium alkoxide may be brought into contact with a magnesium halide before being brought into contact with the electron-donating compound, and the contacting method is the same as in the method (1) above.

■ Contact with halogenated hydrocarbon The contact between the contact material (hereinafter referred to as contact material (2)-1) of the screw alkoxide and the child-donating compound (hereinafter referred to as contact material (2)-1) and the halogenated hydrocarbon is as described above. Similar to method (1) (■), a method of mechanically co-pulverizing a solid or slurry mixture of contact material (2)-1 and a solid or liquid halogenated hydrocarbon, or a method of simply stirring. Among these, a contact method involving mechanical co-pulverization is desirable. Contact article (2)-1 may be cleaned with a suitable cleaning agent, such as an inert hydrocarbon, before being brought into contact with the halogenated hydrocarbon.

The contact ratio between contact material (2)-1 and halogenated hydrocarbon is as follows: magnesium alkoxide 1 in contact material (2)-1
The mole amount is 0.01 to 20 moles of the halogenated hydrocarbon and 0.1 to 20 mole of the halogenated hydrocarbon. The contact conditions such as contact temperature and contact time are preferably the same as in the case of the method (2) above.

■ Contact with titanium compounds Contact of magnesium alkoxide, electron-donating compounds, and halogenated hydrocarbons with titanium compounds is as follows:
It is desirable to carry out the same method as in method (1) (2) above.

Method (3) ■ Contact of magnesium alkoxide/% halogenated hydrocarbon The contact between magnesium alkoxide and halogenated hydrocarbon is carried out in the same manner as in method (p) of (1) above.

The magnesium alkoxide can be brought into contact with the magnesium halide during fusion with the 10-genated hydrocarbon, and the method is the same as in the case (1) above.

(2) Contact with a titanium compound The contact between the contact material obtained in the above-mentioned contact (1) and a titanium compound is carried out in the same manner as in the method (1) (glue) above.

■ Contact with an electron-donating compound Contact between the contact material (hereinafter referred to as contact material (3)) obtained in the above-mentioned contact with the electron-donating compound (hereinafter referred to as "contact material (3)") is performed using an inert hydrocarbon or (J(/or) This can be achieved by a method of mixing 4Wj 4'l' in the presence or absence of a halogenated hydrocarbon, a method of mechanical co-pulverization, and the like.

The contact ratio between the contact wJ (3) and the electron dynamic compound is 001 to 10 moles, more preferably 002 to 10 moles of the electron donating compound per gram atom of titanium in the contact material (3).
It is 5 moles. In the method of bringing hydrocarbons and/or halogenated hydrocarbons into contact with the presence F, when mixing and stirring the hydrocarbons, the solid substance in the contact system is
It is preferable to use liquid substance 1 in an amount such that the temperature is 10 to 300 f, and the contact temperature in this case is 0 to 200 ° C.
Preferably the temperature is 20-150°C, and the contact time is 01-20°C.
0 hours, preferably 0.5 to 10 hours. When co-pulverizing mechanically, the contact material (3) is 100%, and the hydrocarbon is 1 to 100%. In this case, the contact temperature is preferably room temperature to 200°C, and the contact time is preferably 0.1 to 100 hours.

When an electron-donating compound is brought into contact with the hydrocarbon in the absence of the hydrocarbon, it is preferable to use a method of mechanical co-pulverization, in which the contact temperature is room temperature to 200°C, and the contact time is 1 d.
O, 1 to 100 hours is desirable.

Further, the material in contact with the electron-donating compound may be further brought into contact with the titanium compound according to the above-mentioned method (1).

The solid substance that does not contain a liquid substance obtained as described above is mixed with the liquid substance, and the solid substance that contains a liquid substance is separated from the liquid substance to form the catalyst component used in the present invention. However, if necessary, it may be washed with an inert hydrocarbon and then subjected to ethylene copolymerization after drying or in an inert hydrocarbon sludge state.

The catalyst component obtained as described above (hereinafter referred to as -F).

It is called solid component I. ) may be further contacted with an organic aluminum compound. Contact with the organoaluminum compound will be explained below.

The organoaluminum compound has the general formula FtnAtX3-n
(However, R is an alkyl group or an aryl group, X is a halogen atom, an alkoxy group, or a hydrogen atom, and n is 1≦n≦
Any number in the range of 5. ), and
Examples include trialkylaluminum, dialkylaluminum monohalide, monoalkylaluminum dino-1ride, alkylaluminum sesquihalide, dialkylaluminum monoalkoxide, and dialkylaluminum monohydride having 1 to 18 carbon atoms, preferably 2 to 6 carbon atoms. Alkylaluminum compounds or mixtures or complexes thereof are particularly preferred. Specifically, trimethylaluminum, trimethylaluminum, tripropylaluminum, triisobutylaluminum, trihexy! rare! Trialkylaluminum such as reminium, dialkylaluminum monohalide such as dimethylaluminum chloride, diethylaluminum bromide, diethylaluminum bromide, diethylaluminum iodide, diisobutylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, ethylaluminum dichloride, ethylaluminum siaiodide Tide, monoalkylaluminum cibarides such as isobutylaluminum dichloride, alkylaluminum sesquihalides such as ethylaluminum sesquichloride, dimethylaluminum methoxide,
Dialkyl aluminum monoalkoxides such as diethyl aluminum ethoxide, diethyl aluminum phenoxide, dipropylaluminum ethoxide, diisobutyl aluminum ethoxide, diisobutyl aluminum ethoxide, dimethyl aluminum hydride, diethyl aluminum hydride, dipropyl aluminum hydride, diisobutyl aluminum hydride Dialkyl aluminum ramno1 such as
Idride is mentioned.

Among these, dialkyl aluminum motuvalide and 'hVC diethyl aluminum chloride are preferred. These dialkylaluminum monohalides may also be combined with other organoaluminum compounds such as industrially easily available triethylaluminum, triisobutylaluminum, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride, or these. It can be used in combination with a mixture or a complex compound.

The contact between the solid component (1) and the organoaluminum compound is achieved by a contact method such as mixing and stirring, mechanical co-pulverization, etc. in the presence or absence of an inert hydrocarbon. As the organic aluminum compound, any of the above compounds can be used, but trialkylaluminum and dialkylaluminum halide are more preferred. The proportion of the organic aluminum compound used in the contact between the solid component (I) and the organoaluminum compound is 0.05 to 1 of the organic aluminum compound per 1 gram atom of titanium in the solid component I.
0 gmole, preferably 01-5 gmmol.

When contacting is carried out by mixing and stirring in the presence of an inert hydrocarbon, 1 to 10% of the solid component I is added to the inert hydrocarbon 1.
600v, more preferably 15-2001. The contact temperature is -50U to 150℃, more preferably -20℃
~100°C. In this case, the contact method is to add a predetermined amount of the organoaluminum compound to isoisomer component I for 1 minute to 1 minute.
Gradually add and contact for 0 hours, preferably 5 minutes to 5 hours, and continue for 01 to 20 hours, preferably 0.5 to 5 hours.
It is preferable to continue stirring for 10 hours to keep them in contact.If they are brought into contact for a short time of less than 1 minute, the solid component (2) will split into fine particles, making it difficult to handle the solid component in the subsequent preparation. When an olefin is polymerized using a polymer, a large amount of finely powdered olefin polymer is produced, which is undesirable because it adversely affects the physical properties of the polymer, the productivity of the polymer, and the like.

In the case of mechanical co-grinding and contact, the solid component 1100
It is desirable to use 1 to 100 parts of ageless hydrocarbon per 1F, and in this case, the contact temperature is preferably room temperature to 100°C, and the contact time is preferably 5 minutes to 2 hours. In the case of contacting without using an inert hydrocarbon, it is preferable to contact by mechanical co-pulverization, and the contact temperature at that time is room temperature to 100 ° C.
The contact time is preferably 5 minutes to 2 hours.

The solid substance obtained as above (hereinafter referred to as F, solid component ■) is separated from the reed or liquid substance, washed with an inert hydrocarbon as necessary, and dried. Provided for ethylene copolymerization.

The solid component I may be brought into contact with the olefin and the organoaluminum compound (hereinafter referred to as pretreatment) before use. Moreover, the preparation of solid component II by contacting solid component I with an organoaluminum compound can be carried out in the presence of an olefin.

Pretreatment can be carried out in the presence of an inert hydrocarbon,
It is desirable to first contact the solid component (1) with the olefin and then with the organoaluminum compound. The treatment temperature is generally 0 to 80°C.

A polymer is generated by the pretreatment and coexists with the catalyst component by adding it to the catalyst component (solid component ■ and solid component ■), but its 'jit is 0.05~
It is desirable to set it to 102.

The pretreatment has the effect of preventing the catalyst component and the final polymer from becoming fine, making it easier to adjust the particle size, and improving the mechanical strength of the catalyst component.

Ethylene Copolymerization Catalyst The copolymerization catalyst of the present invention is a combination of a catalyst component (isomer component I or solid component ①) and an organoaluminum compound.

The organoaluminum compound may be any of the above-mentioned compounds used in preparing the solid component (1), but among them, trialkylaluminum compounds, particularly triethylaluminum and triisobutylaluminum, are preferred. These trialkylaluminums may also be combined with other organoaluminum compounds such as industrially easily available diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquichloride, diethylaluminum ethoxide, diethylaluminum hydride, or mixtures or complexes thereof. It can be used in combination with other compounds.

Furthermore, the organoaluminum compound may be used alone or in combination with an electrodynamic compound. The electron-donating compound may be the same as the compound used in preparing the catalyst component.

The electron-donating compound may be used when an organoaluminum compound is used in combination with a catalyst component, or may be used after being brought into contact with the organoaluminum compound in advance.

The amount of organoaluminum compound used relative to the catalyst component is
Usually 1 to 20 per gram atom of titanium in the catalyst component.
00 gmol, especially 20 to 500 gmol.

The ratio of the organoaluminum compound to the electron-donating compound is selected within the range of 0.1 to 40, preferably 1 to 25, gram atoms of the organoaluminum compound as aluminum per mole of the electron-donating compound.

Method for producing ethylene copolymer composition The composition obtained by the method of the present invention is a melt inotex obtained by copolymerizing ethylene and α-olefin in the presence of the above-mentioned catalyst.
/10 minutes, a copolymer (hereinafter referred to as component A) with a density of 09 UO ~ 0.940 f/lyn" and Melt Intex 50 ~ 2.000 f/1yn3, a density of 0.920 ~
0.950? /cm" copolymer (hereinafter referred to as component B). The method for producing component A and component B will be explained below.

Production method of component A The α-olefin used in the copolymerization includes propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and the like.

The polymerization reaction can be carried out either continuously or batchwise, but a continuous method is preferred.

The polymerization reaction is preferably carried out in an inert hydrocarbon in a liquid phase, and can be carried out in the presence or absence of a gas phase. Inert hydrocarbon, fit, normal butano, isobutane, normal pentane, isopenkune,
Examples include saturated aliphatic hydrocarbons such as hexane, heptane, and octane, saturated alicyclic hydrocarbons such as cyclopenkune and cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene, and mixtures thereof can also be used. Considering the solubility of the inert hydrocarbon copolymer and the difficulty of separation operation, light saturated aliphatic hydrocarbons such as normal butane and inbutane are preferable.

The polymerization temperature is usually -20 to -1-150°C, preferably 50 to 90°C, and the polymerization pressure is usually 1 to 60 atm.

Melt index determined by component A (o, o o
i~1 f/10 min) is the hydrogen supply amount, and the density (0
, 900 to 0.940 f/Crn3) can be adjusted by adjusting the amount of α-olefin supplied. If the melt index is less than o, ooi 1/10 min, the melt index of the composition will decrease and the moldability will decrease. Moreover, if it exceeds 11/10 minutes, the molecular weight distribution will not be widened, and the effect of improving moldability will not be sufficient. If the density falls below the above range, the copolymer becomes sticky and the composition becomes difficult to handle. In addition, if the metal exceeds the above range, physical properties such as resistance to environmental stress cracking will deteriorate.

Manufacturing method of component B In the same manner as the manufacturing method of component A, the melt index is 50 to 2.00Of/10 minutes, the density is 0, 910 to 0.
950 t/rm3 of B Jj)4 minutes is produced.

If the melt index of component B is less than 50 f/10 minutes, the molecular weight distribution will not be widened and the effect of improving moldability will not be sufficient. Increasing it by more than 2.000 f'/10 minutes compromises the mechanical strength of the composition. Moreover, if the density exceeds the above range, the composition becomes sticky, and if it becomes too thick, the physical properties such as resistance to environmental stress cracking deteriorate.

The composition obtained by the method of the present invention is obtained by mixing component A and component B obtained above. A
The mixing ratio of the component and the B component is arbitrary, but preferably the A component is 10 to 60% and the B component is 40 to 90% by weight.

It is important that the A component and the B component are thoroughly mixed.
If mixing is insufficient, the object of the present invention cannot be fully achieved. Therefore, it is desirable to mix the two by melting and kneading them. For mixing, a general mixing machine such as a Banbury Mixer 1 extruder can be used, and a Brabender or the like is used in the case of a small amount.

The composition of the present invention obtained by smelting has a temperature of 0.01 to 30F.
/10 minutes 7I, having a density of 0910 to 09401/m3, and in particular, a mixture of A component and B component in the above ratio has a shear rate of 751.0.1 rad/m3 at 230°C.
The ratio of melt viscosities in s and 500 rad/s η0
．． The value obtained by converting 1/η500 to melt intex 1 f/10 min (η01 /η500)MI=1 (hereinafter -
To, [η] and 1I161 myself. ) has a wide molecular weight distribution of 20 or more.

Note that [η] is a value obtained using the following equation.

Effects of the Invention The composition obtained by the method of the present invention has a wide molecular weight distribution, has both the good mechanical properties of the high molecular weight component and the good fluidity during molding of the low molecular weight component, has strong tear strength, and has good moldability. It is characterized by good

EXAMPLES Next, the present invention will be specifically explained using examples and reference examples. In addition, the percentages (%9) shown in Examples and Reference Examples
are duplicates unless otherwise specified.

Melt intex of polymer (r, i I ) Ha,
According to ASTM-DI238, temperature 190°C, load 2.
Measured with 16 K9. Normal hexane solubility (nHxS), which indicates the proportion of solvent-soluble polymer in the polymer
is the commonly understood proportion of polymer when the polymer is extracted in boiling normal water for 95 hours using an improved Soxhlet extractor. The specific activity (Hsp) of the catalyst is I! l!
! ! MVj component 12, polymerization time 1 hour, ethylene concentration 1 mole during polymerization, amount of polymer produced per ethylene partial pressure 1 atm (r) f: Indicates. When using a pretreated catalyst component, the specific activity was calculated by substituting the catalyst component before pretreatment.

Bulk density of ethylene copolymer (BD is ASTM Dl 8
Measured according to 95-69 method AK.

The density of the ethylene copolymer was determined by the density gradient tube method according to JIS K-6760.

Environmental stress fracture resistance (ES(l()) is ASTM D16
60 using a 10% nonionic aqueous solution according to 93-70.
Measured at °C. Tear strength is ASTM D1922-67
Measured according to The sample piece used was a film with a thickness of about 100 μm.

The tear strength is the value corrected by the thickness (f/mj, 1;
1 ml-254μ).

Melt viscosity was measured using Melt Viscoelasticity Measuring Device K manufactured by Geontric.
Using a
ll11 was determined. [η] was determined from this measurement result.

Catalyst components (conditioning of υ) Commercially available magnesium jetoxide 582 and anhydrous magnesium chloride 48 were mixed with stainless steel (SUS51) with a diameter of 12 cm.
6) A mill pot made of stainless steel (SUS316) with an internal volume of 1 ton containing 640 balls was placed in a mill pot made of stainless steel (SUS316), and the mill pot was attached to a shaker and shaken for 4 hours. 2 /
Mf, C12/C2CLt4 (molar ratio) = 1/110.
24) was added and co-pulverized for 15 hours, and further ethyl benzoate 151 was added and co-pulverized for 15 hours to obtain a pulverized product.

The pulverized product 1007 obtained above was heated for 5 minutes under nitrogen gas atmosphere.
00 me flask and add 100r of toluene to it.
ne and 50 tnt of ditane tetrachloride were added and brought into contact with each other by stirring at 95°C for 2 hours. Excess liquid was removed and the solid material was diluted with 150rnl of n-hexane at 65°C for 6 hours.
It was washed twice and dried under reduced pressure at 50° C. for 1 hour to obtain a catalyst component (1) with a titanium content of 3.2%.

Preparation of catalyst component (2) Catalyst component (2) was prepared in the same manner as catalyst component (1) except that magnesium dilatate was not used.

Preparation of Catalyst Component (3) Catalyst Component (1) 5 r was heated for 200-min under nitrogen gas atmosphere.
into a flask, and 101 mg' of n-hebutane was added thereto to form a slurry. While stirring this slurry at room temperature, 5.5 mmol of triethylaluminum A was gradually added dropwise over 1 hour at J1-1, and stirring was continued for 2 hours after the dropwise addition. Next, remove the upper 1st culture solution and add 100 ml each of n-
It was washed four times with hexane and further dried to obtain catalyst component (3).

Catalyst component (1) 5 f in a nitrogen gas atmosphere, 500
- into a flask, 150 m7 of n-hexane! was added to make a slurry. While stirring this slurry at room temperature, 4.85 parts by weight and 7 moles of triisobutylaluminum were added to 2
The mixture was added dropwise over a period of time, and stirred for 1 hour after the droplets were added. Ethylene was then introduced at room temperature and under normal pressure, and the catalyst Jli, min (1) was added.
1? 0.62 of ethylene was produced per contact. After that, the supernatant liquid was removed and washed 4 times with 150 g of n-hexane.
Further drying was performed to prepare catalyst component (4).

Production of copolymer (1) A stainless steel (SUS5) with an internal volume of 1.5 tons equipped with an agitator.
2) in a nitrogen gas atmosphere, catalyst component (1) 12747, triisobutylaluminum 0.
Add 7 mmol and 700 g of isobutane to bring the polymerization system to 8
The temperature was raised to 5°C. Next, hydrogen partial pressure is 0.50 Kg+/c
After introducing hydrogen gas so that the pressure is 3K17cm, ethylene is introduced until the partial pressure of ethylene becomes 3K17cm, and then
- Added 101 butenes. Polymerization was carried out for 60 minutes while continuously supplying ethylene so that the total pressure of the polymerization system was kept constant. Isobutane, unreacted ethylene and 1
- Purge the butene and take out the self-stamping powdered polymer;
Dry under reduced pressure at 70°C for 10 hours to MI 0.1F.
/Io min, density 0.925 f/crn3 ethylene-
1,621 1-butene copolymers were obtained.

Production of copolymer (■Zil (XvII)) Depending on the catalyst components and polymerization conditions shown in Table 1, the copolymer (
Copolymers (11) to (I) were prepared in the same manner as I).
JI) was obtained. The physical properties of the obtained copolymer are shown in Table 1.

Reference Example 1 (Production of composition) Copolymer (i) 15 t and copolymer (y) 35 y
and further added 0.05 parts by weight of BHT (trade name, antioxidant), 0.1 parts by weight of Irganox 1010 (trade name, antioxidant) and 0 parts by weight of calcium stearate as additives per 100 parts by weight of the mixture. .25 parts by weight were added and melt-kneaded using a Brabender. The operating conditions for the Brabender are: temperature 190°C, crosstalk time 5 minutes, rotation M 50 r.
It was pm.

The physical properties of the obtained composition were measured and the results are shown in Table 2.

Reference Examples 2 to 12 (Production of Compositions) Various copolymers were mixed in the mixing proportions shown in Table 2 in the same manner as in Reference Example 1 to prepare various compositions. The physical properties of the obtained composition were as shown in Table 2. As is clear from the table, the ethylene copolymer composition of the present invention has a wide molecular weight distribution, strong tear strength, and good moldability.

Claims (1)

[Claims] 1) Copolymerizing ethylene and α-olefin using a catalyst component formed by contacting a magnesium alkoxide, a norogenated hydrocarbon, an electron-donating compound, and a titanium compound, and a catalyst formed of an organoaluminum compound. Method for producing ethylene copolymer.